JPH0485305A - Removal of low-molecular component from melt-processable tetrafluoroethylene copolymer - Google Patents
Removal of low-molecular component from melt-processable tetrafluoroethylene copolymerInfo
- Publication number
- JPH0485305A JPH0485305A JP20069390A JP20069390A JPH0485305A JP H0485305 A JPH0485305 A JP H0485305A JP 20069390 A JP20069390 A JP 20069390A JP 20069390 A JP20069390 A JP 20069390A JP H0485305 A JPH0485305 A JP H0485305A
- Authority
- JP
- Japan
- Prior art keywords
- melt
- copolymer
- tetrafluoroethylene copolymer
- tetrafluoroethylene
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 17
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 11
- 229910052731 fluorine Chemical group 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 7
- 239000011737 fluorine Chemical group 0.000 claims description 7
- -1 alkyl vinyl ether Chemical compound 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000005192 alkyl ethylene group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 5
- 230000004580 weight loss Effects 0.000 abstract description 4
- 238000005187 foaming Methods 0.000 abstract description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract 2
- 238000000605 extraction Methods 0.000 description 20
- 239000008188 pellet Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- UJIGKESMIPTWJH-UHFFFAOYSA-N 1,3-dichloro-1,1,2,2,3-pentafluoropropane Chemical compound FC(Cl)C(F)(F)C(F)(F)Cl UJIGKESMIPTWJH-UHFFFAOYSA-N 0.000 description 1
- 101150050425 CCC2 gene Proteins 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical class FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/04—Fractionation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、テトラフルオロエチレンと少なくとも１種の
エチレン性不飽和コモノマーからなる溶融加工可能な共
重合体中の低分子量体を除去する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for removing low molecular weight compounds in a melt-processable copolymer of tetrafluoroethylene and at least one ethylenically unsaturated comonomer. .
［従来の技術］
テトラフルオロエチレンとへキサフルオロプロピレンと
の共重合体（以下、ＦＥＰという）やテトラフルオロエ
チレンとパーフルオロ（プロピルヒニルエーテル）との
共重合体（以下、ＰＦＡという）は、溶融成形可能なフ
ッ素樹脂であり、その優れた耐熱性、耐薬品性、電気特
性などをいかして、電線、バイブ、チューブ、フィルム
、耐蝕ライニング、つエバーキャリアなどとして、電気
、薬品、半導体分野などで広く用いられている。[Prior Art] A copolymer of tetrafluoroethylene and hexafluoropropylene (hereinafter referred to as FEP) and a copolymer of tetrafluoroethylene and perfluoro(propyl hinyl ether) (hereinafter referred to as PFA) are It is a moldable fluororesin, and by taking advantage of its excellent heat resistance, chemical resistance, and electrical properties, it is used in electric wires, vibrators, tubes, films, corrosion-resistant linings, Evercarriers, etc. in the electrical, pharmaceutical, and semiconductor fields. Widely used.
これらのテトラフルオロエチレン共重合体は、例えば、
特公昭４８−２０７８８号公報に開示されているような
乳化重合や、特公昭６２−３６０４５号公報に開示され
ているような水性懸濁重合によって製造されるが、いず
れの場合にも、通常、オリゴマーと呼ばれる低分子量体
（数平均分子量が、通常約１０００以下）がある程度副
生ずる。These tetrafluoroethylene copolymers are, for example,
It is produced by emulsion polymerization as disclosed in Japanese Patent Publication No. 48-20788 or aqueous suspension polymerization as disclosed in Japanese Patent Publication No. 62-36045, but in either case, usually A certain amount of low molecular weight substances called oligomers (number average molecular weight is usually about 1000 or less) are produced as by-products.
［発明が解決しようとする課題］
この低分子量体は本来望ましからざるものであり、例え
ば高温にさらされる溶融成形時に揮発して、成形ダイス
やフィルム成形ロールに凝固付着したり、成形品の発泡
の原因となることがある。[Problems to be Solved by the Invention] This low molecular weight substance is inherently undesirable; for example, it volatilizes during melt molding exposed to high temperatures, solidifies and adheres to molding dies and film molding rolls, or causes damage to molded products. May cause foaming.
また高度なりリーン度が要求される半導体関連分野にお
いてパーティクル（ダスト）の原因ともなりうる。更に
、低分子量体が多いと耐ストレスクラック性のような機
械的強度を低下せしめるといった問題が派生してくる。It can also cause particles (dust) in semiconductor-related fields that require a high degree of leanness. Furthermore, if the amount of low molecular weight substances is large, problems arise such as a decrease in mechanical strength such as stress crack resistance.
従来、テトラフルオロエチレン共重合体からの低分子量
体除去は試されていなかった。Conventionally, no attempt has been made to remove low molecular weight substances from tetrafluoroethylene copolymers.
ＦＥＰやＰＦＡといった大部分がパーフルオロ化された
テトラフルオロエチレン共重合体は極めて優れた耐薬品
性と耐溶媒性を有している。これはＣ−Ｆ結合力が大き
いことと、Ｆ原子かＣ−Ｃ結合の周囲を隙間なく埋めて
いてＣ−Ｃ結合に対する他物質の攻撃を防いでいるため
である。従って、これらのポリマーは２００°Ｃ以上の
高温でパーフルオロアミンやパーフルオロカーボンに一
部溶解する以外は、通常の条件下ではほとんど溶解しな
い。重合度の充分に高いポリマーと同様にこれらのオリ
ゴマーもまた一般溶媒に対し溶解度が極めて低い。した
がって、この不溶性の故に通常用いられるポリマーから
のオリゴマー除去方法が適用できない、即ち、洗浄法、
抽出法、再沈澱法、イオン交換樹脂による分離といった
、何らかの溶媒に溶解させる必要のある手段は使えない
と考えられていた。Mostly perfluorinated tetrafluoroethylene copolymers such as FEP and PFA have extremely excellent chemical and solvent resistance. This is because the C--F bond strength is large and the F atom fills the area around the C--C bond without any gaps, thereby preventing attacks by other substances on the C--C bond. Therefore, these polymers hardly dissolve under normal conditions, except for some dissolution in perfluoroamines and perfluorocarbons at high temperatures of 200°C or higher. Like polymers with a sufficiently high degree of polymerization, these oligomers also have extremely low solubility in common solvents. Therefore, due to this insolubility, commonly used methods for removing oligomers from polymers cannot be applied, i.e., washing methods,
It was thought that methods that required dissolution in some kind of solvent, such as extraction methods, reprecipitation methods, and separation using ion exchange resins, could not be used.
本発明は、既に重合の終了したテトラフルオロエチレン
共重合体から低分子量体を効率よく除去する方法を提供
しようとするものである。The present invention aims to provide a method for efficiently removing low molecular weight substances from a tetrafluoroethylene copolymer that has already been polymerized.
［課題を解決するための手段］
本発明者らは、ＰＥＰ、ＰＦＡなどのテトラフルオロエ
チレン共重合体と親和性の高いフッ素系溶媒が、適当な
加熱により共重合体中の低分子量体を溶解し得ることを
見い出し本発明を完成するに至った。[Means for Solving the Problems] The present inventors have discovered that a fluorine-based solvent having high affinity with tetrafluoroethylene copolymers such as PEP and PFA dissolves low molecular weight substances in the copolymer by appropriate heating. They have discovered that it is possible to do so and have completed the present invention.
本発明は、テトラフルオロエチレンと少なくとも１種の
エチレン性不飽和コモノマーからなる溶融成形可能なテ
トラフルオロエチレン共重合体をフッ素系溶媒で抽出す
ることから成るテトラフルオロエチレン共重合体から低
分子量体を除去する方法に関する。The present invention involves extracting a melt-formable tetrafluoroethylene copolymer consisting of tetrafluoroethylene and at least one ethylenically unsaturated comonomer with a fluorinated solvent to obtain a low molecular weight substance from a tetrafluoroethylene copolymer. Regarding how to remove.
エチレン性不飽和コモノマーとして、パーフルオロ（Ｃ
，〜ＣＩＯアルキルエチレン）、式：％式％）
１式中、Ｘは水素またはフッ素、ａは０〜４、ｂは０〜
７の数を表わす。］
で示されるフルオロ（アルキルヒニルエーテル）、およ
びこれらの組み合わせか挙げられる。ヘキサフルオロプ
ロピレン、パーフルオロ（メチルビニルエーテル）、パ
ーフルオロ（エチルビニルエーテル）、パーフルオロ（
プロピルヒニルエーテル）、パーフルオロ（プチルヒニ
ルエーテル）、ＣＦ２＝ＣＦ−ＯＣＦ、ＣＦ−０−ＣＦ
ｔＣＦＩＣＦ３Ｆ３
が特に好ましい。Perfluoro (C
, ~CIO alkylethylene), formula: % formula %) In the formula, X is hydrogen or fluorine, a is 0-4, b is 0-
Represents the number 7. ] and combinations thereof. Hexafluoropropylene, perfluoro(methyl vinyl ether), perfluoro(ethyl vinyl ether), perfluoro(
propylhinyl ether), perfluoro(butylhinyl ether), CF2=CF-OCF, CF-0-CF
Particularly preferred is tCFICF3F3.
フッ素系溶媒は、１〜５個の炭素原子と少なくとも１個
のフッ素原子を有し、さらに塩素原子、水素原子、酸素
原子、臭素原子およびチッ素原子から成る群からから選
択された少なくとも１個の原子を場合により有する化合
物、またはこれら化合物の組み合わせである。フッ素系
溶媒の具体例としては、
ＣＣｆｆ３Ｆ（Ｒ−１１）、ＣＣｆｆ、Ｆ、（Ｒ−１２
）、ＣＨＣＱＦｔＣＲ−２２）、ＣＣＱＩＦ ＣＣＣ２
Ｆ （Ｒ−１１２）、ＣＣＱ２Ｆ’ＣＧ（ｌＦｔＣＲ−
１１３）、ＣＣ（２ＦｔＣＣ＆Ｆ、（Ｒ−１１４）、Ｃ
ＨＣｌ２ｔＣＦ −（Ｒ１２３）、ＣＨ３ＣＣｌ２Ｆ（
Ｒ−１４ｌｂ）、ＣＨ３ＣＣｌ２Ｆ ｔ（Ｒ１４２ｂ）
、ＣＨｔ Ｆ ＣＦ ｓ（Ｒｌ ３４ ａ）、ＣＨｉＣ
ＨＦｔ（Ｒ１５２ａ）、ＣＦ３ＣＰ、ＣＨ，ＯＨ，ＣＦ
、−ＣＦ、、ＣＣＱ３Ｆ（Ｒ−１３）、ＣＢｒＣＦ、−
ＣＰ。The fluorine-based solvent has 1 to 5 carbon atoms and at least one fluorine atom, and further has at least one fluorine atom selected from the group consisting of chlorine atom, hydrogen atom, oxygen atom, bromine atom, and nitrogen atom. or a combination of these compounds. Specific examples of fluorine-based solvents include CCff3F (R-11), CCff, F, (R-12
), CHCQFtCR-22), CCQIF CCC2
F (R-112), CCQ2F'CG (lFtCR-
113), CC (2FtCC&F, (R-114), C
HCl2tCF - (R123), CH3CCl2F (
R-14lb), CH3CCl2F t(R142b)
, CHt F CF s (Rl 34 a), CHiC
HFt (R152a), CF3CP, CH, OH, CF
, -CF, , CCQ3F (R-13), CBrCF, -
C.P.
ＣＱＦ＊、ＣＢｒＦ３、ＣＦ、（Ｒ−１４）、ＣＨＦ５
（Ｒ２３）、ＣＢ ｒ Ｆ ｔ ＣＢ ｒ Ｆ ｔ、Ｃ
ＣＱＦｔＣＦ３（Ｒ１１５）、ＣＦ ３ＣＦ ＊（Ｒ１
１６）、ＣＦ、ＣＦ ｔ ＣＨＣＱ−（Ｒ２２５ｃａ）
、ＣＣＱＦ、ＣＨ３ＣＣｌ２Ｆ（Ｒ−２２５ｃｂ）、パ
ーフルオロ（トリブチル）アミンおよびこれらの組み合
わせが挙げられる。CQF*, CBrF3, CF, (R-14), CHF5
(R23), CB r F t CB r F t, C
CQFtCF3(R115), CF3CF*(R1
16), CF, CF t CHCQ-(R225ca)
, CCQF, CH3CCl2F (R-225cb), perfluoro(tributyl)amine and combinations thereof.
Ｒ−１１３およびＲ−１１４が特に好ましい。R-113 and R-114 are particularly preferred.
抽出に供する共重合体の形態は、粉末、フレーク、立方
体、ペレットまたは成形品であることができる。後の抽
出液との濾別の利便さからペレットが好ましい。The form of the copolymer subjected to extraction can be powder, flakes, cubes, pellets or molded articles. Pellets are preferred from the standpoint of convenience in subsequent filtration separation from the extract.
抽出には、通常、底部に抽出液抜き出し口の付いた温調
ジャケット付き耐圧容器（オートクレーブ）が用いられ
るが、これに相当する容器（例えば滅菌器）であれば限
定はされない。抽出温度と抽出時間は抽出溶媒および抽
出に供する共重合体の形態により選ばれ、特に限定され
ない。抽出温度は抽出溶媒の沸点以上であることが好ま
しい。抽出時間は１０時間以上であることが好ましい。For extraction, a pressure-resistant container with a temperature-controlled jacket (autoclave) with an extraction liquid outlet at the bottom is usually used, but there is no limitation as long as it is an equivalent container (for example, a sterilizer). The extraction temperature and extraction time are selected depending on the extraction solvent and the form of the copolymer to be extracted, and are not particularly limited. The extraction temperature is preferably higher than the boiling point of the extraction solvent. Preferably, the extraction time is 10 hours or more.
抽出に供される共重合体と抽出溶媒の仕込量も特に限定
されない。抽出効率の点から抽出溶媒は共重合体の同質
量以上が好ましい。The amounts of the copolymer and extraction solvent used for extraction are also not particularly limited. From the point of view of extraction efficiency, the extraction solvent preferably has an amount equal to or more than the same mass as the copolymer.
抽出終了後の抽出液と被抽出共重合体の分離は通常の濾
別によって行われる。即ち、濾紙やガラスフィルター、
メツシュ金網等を用いて行われる。After the extraction is completed, the extract and the copolymer to be extracted are separated by conventional filtration. i.e. filter paper or glass filter,
This is done using mesh wire mesh, etc.
濾別は抽出終了後冷却することなく、抽出温度のままで
迅速に行わなければならない。抽出液を冷却してしまう
と、せっかく溶けていた低分子量体が、再び固体として
析出することがあるからであ抽出によって除去された低
分子量体の割合（重量％）は、抽出液を蒸発して残る固
形物（低分子量体）の質量を測定することによって算出
される。Filtration must be carried out quickly at the extraction temperature without cooling after the extraction is complete. If the extract is cooled, the dissolved low molecular weight substances may precipitate out as solids again.The proportion (wt%) of the low molecular weight substances removed by extraction is It is calculated by measuring the mass of the solid matter (low molecular weight body) that remains.
共重合体質ｉ１（ｋｇ）
本発明によれば、通常、共重合体に対して０００１重量
％以上の低分子量体が除去できる。除去される低分子量
体が多いほど被抽出共重合体の物性が良好になるので好
ましくは０．０１重量％以上の低分子量体を除去するの
がよい。抽出によって除去される低分子量体の数平均分
子量は、通常、１０００以下である。Copolymer composition i1 (kg) According to the present invention, usually 0001% by weight or more of low molecular weight substances can be removed from the copolymer. The physical properties of the copolymer to be extracted become better as more low molecular weight substances are removed, so it is preferable to remove 0.01% by weight or more of low molecular weight substances. The number average molecular weight of the low molecular weight substance removed by extraction is usually 1000 or less.
［発明の好ましい態様］ 次に、実施例を示し、本発明を具体的に説明する。[Preferred embodiment of the invention] Next, the present invention will be specifically explained with reference to Examples.
実施例１
テトラフルオロエチレン／パーフルオロ（プロピルビニ
ルエーテル）共重合体（Ｐ Ｆ ＡＸ３８０℃における
溶融粘度３．０ＸｌＯ’ボイズ、パーフルオロ（プロピ
ルビニルエーテル）含有量的３．５重量％）の押出しペ
レット（直径２〜３ｘｍ、高さ３〜４■の円柱状）３０
．６ｋｇとフッ素系溶媒ＣＣＩＬＦＣＣｌＦ２ＣＣｌＦ
２Ｆｔ（Ｒ−１１３、沸点４７．６℃）５０．０＆ｇを
内容積的１６０Ｑの撹拌機つきオートクレーブに仕込み
密閉した。ｉｏｏｒｐｍで撹拌しながら、８０℃で１５
時間加熱した。このときオートクレーブ内の圧力は２
、５ ｋｇ／ ｃｍ” Ｇまで上昇した。内温８０℃の
ままメツシュ金網をはさんだオートクレーブ底部抜き出
しバルブをゆっくり開け、Ｒ１１３抽出液全量をポリエ
チ容器に移した。Ｒ−１１３抽出液をエバポレイターで
蒸発したところ１８．３９の白色粉末が得られた。この
白色粉末は赤外分光分析した結果、テトラフルオロエチ
レン／パーフルオロ（プロピルビニルエーテル）共重合
体の低分子量体であることがわかった。ＰＦＡペレット
からは抽出で０．０６重量％の低分子量体が除去できた
ことになる。このＲ，−１１３抽出ベレツトと未処理ペ
レットを用いてフッ酸浸漬によるパーティクル溶出試験
を行った。Example 1 Extruded pellets (diameter) of tetrafluoroethylene/perfluoro(propyl vinyl ether) copolymer (melt viscosity at 380°C P 2-3xm, height 3-4 cm) 30
．． 6 kg and fluorinated solvent CCILFCClF2CClF
50.0g of 2Ft (R-113, boiling point 47.6°C) was charged into an autoclave with an internal volume of 160Q and equipped with a stirrer, and the autoclave was sealed. 15 at 80°C with stirring at ioorpm.
heated for an hour. At this time, the pressure inside the autoclave is 2
, 5 kg/cm"G. While keeping the internal temperature at 80°C, the outlet valve at the bottom of the autoclave sandwiched between mesh wire meshes was slowly opened, and the entire amount of the R113 extract was transferred to a polyethylene container. The R-113 extract was transferred to a polyethylene container. Upon evaporation, a white powder of 18.39 was obtained.As a result of infrared spectroscopic analysis, this white powder was found to be a low molecular weight product of tetrafluoroethylene/perfluoro(propyl vinyl ether) copolymer.PFA This means that 0.06% by weight of low molecular weight substances could be removed from the pellets by extraction.A particle elution test was conducted by immersion in hydrofluoric acid using this R,-113 extracted pellet and the untreated pellets.
パーティクル溶出試験は以下のようにして行った。The particle elution test was conducted as follows.
よく洗浄したポリエチ瓶に５０％フッ酸５００９を入れ
る。ＰＦＡペレット１２５ｇを浸漬し、直ちにフッ酸中
のパーティクル（直径０．３μ１以上のパーティクル）
の個数をパーティクルカウンター（リオン社製ＫＬ−２
１）によって測定する。浸漬４日後および１６日後のパ
ーティクル個数を測定し、浸漬直後を１とした場合の増
加率を算出する。Pour 50% hydrofluoric acid 5009 into a well-washed polyethylene bottle. Immerse 125g of PFA pellets and immediately remove particles (particles with a diameter of 0.3μ1 or more) in hydrofluoric acid.
Count the number of particles using a particle counter (Rion KL-2).
Measure according to 1). The number of particles is measured after 4 days and 16 days of immersion, and the rate of increase is calculated when the number immediately after immersion is set to 1.
パーティクル溶出試験の結果を下表に記す。The results of the particle elution test are shown in the table below.
Ｒ−１１３抽出ペレツトは未処理ペレットに比ペパーテ
ィクル増加率が小さく、低分子量体を除去した効果が表
われている。The R-113 extracted pellets had a smaller particle increase rate than the untreated pellets, indicating the effect of removing low molecular weight substances.
また、Ｒ−１１３抽出ペレツトと未処理ペレットを用い
て加熱減量テストも行った。加熱減量テストは以下のよ
うにして行った。A heat loss test was also conducted using R-113 extracted pellets and untreated pellets. The heating loss test was conducted as follows.
アルミカップにＰＦＡペレットｌｏｇを秤量し、電気炉
中３８０℃で３時間および５時間加熱する。Weigh the PFA pellet log into an aluminum cup and heat it in an electric furnace at 380° C. for 3 and 5 hours.
加熱後、室温まで冷却して後、これを秤量し、ＰＦＡペ
レットに対する重量減少率を算出する。加熱減量テスト
の結果を下表に記す。After heating and cooling to room temperature, it is weighed and the weight loss rate relative to the PFA pellet is calculated. The results of the heating loss test are shown in the table below.
Ｒ−１１３抽出ペレツトは、未処理ペレットに比べ重量
減少率が小さく、低分子量体を除去した効果が表れてい
る。The R-113 extracted pellets had a smaller weight loss rate than the untreated pellets, demonstrating the effect of removing low molecular weight substances.
［発明の効果コ
本発明によれば、難溶性テトラフルオロエチレン共重合
体から簡易に低分子量体を除去することができる。低分
子量体を除去したテトラフルオロエチレン共重合体は成
形性、クリーン度、機械物性などの点で優れている。溶
融成形時において、重量減少が小さく、さらに発泡およ
び金型付着が生じない。共重合体からのパーティクル（
ダスト）放出量が少ない。また、共重合体の機械的強度
が高い。[Effects of the Invention] According to the present invention, low molecular weight substances can be easily removed from a sparingly soluble tetrafluoroethylene copolymer. Tetrafluoroethylene copolymers from which low molecular weight components have been removed are excellent in terms of moldability, cleanliness, mechanical properties, etc. During melt molding, weight loss is small, and foaming and mold adhesion do not occur. Particles from copolymer (
Dust) emission amount is small. Additionally, the copolymer has high mechanical strength.
低分子量体を除去したテトラフルオロエチレン共重合体
は、半導体分野におけるウェハーキャリアとして特に有
用である。Tetrafluoroethylene copolymers from which low molecular weight components have been removed are particularly useful as wafer carriers in the semiconductor field.
特許出願人ダイキン工業株式会社Patent applicant Daikin Industries, Ltd.
Claims (1)
ン性不飽和コモノマーからなる溶融加工可能なテトラフ
ルオロエチレン共重合体をフッ素系溶媒で抽出すること
から成るテトラフルオロエチレン共重合体から低分子量
体を除去する方法。 ２、エチレン性不飽和コモノマーが、パーフルオロ（Ｃ
＿１〜Ｃ＿１＿０アルキルエチレン）、式：▲数式、化
学式、表等があります▼ ［式中、Ｘは水素またはフッ素、ａは０〜４、ｂは０〜
７の数を表わす。］ で示されるフルオロ（アルキルビニルエーテル）、また
はこれらの組み合わせである請求項１記載の方法。 ３、フッ素系溶媒が、１〜５個の炭素原子と少なくとも
１個のフッ素原子を有し、さらに塩素原子、水素原子、
酸素原子、臭素原子およびチッ素原子から成る群からか
ら選択された少なくとも１個の原子を場合により有する
化合物、またはこれら化合物の組み合わせからなる請求
項１記載の方法。 ４、エチレン性不飽和コモノマーが、ヘキサフルオロプ
ロピレンまたはパーフルオロ（プロピルビニルエーテル
）である請求項１記載の方法。 ５、フッ素系溶媒がＣＣｌ＿２ＦＣＣｌＦ＿２またはＣ
ＣｌＦ＿２ＣＣｌＦ＿２である請求項１記載の方法。[Scope of Claims] 1. A tetrafluoroethylene copolymer obtained by extracting a melt-processable tetrafluoroethylene copolymer consisting of tetrafluoroethylene and at least one ethylenically unsaturated comonomer with a fluorinated solvent. Method for removing low molecular weight substances. 2. The ethylenically unsaturated comonomer is perfluoro(C
_1~C_1_0 alkylethylene), formula: ▲Mathematical formula, chemical formula, table, etc.▼ [In the formula, X is hydrogen or fluorine, a is 0-4, b is 0-
Represents the number 7. ] The method according to claim 1, wherein the fluoro(alkyl vinyl ether) is represented by: 3. The fluorine-based solvent has 1 to 5 carbon atoms and at least one fluorine atom, and further contains a chlorine atom, a hydrogen atom,
2. The method of claim 1, comprising a compound optionally containing at least one atom selected from the group consisting of oxygen, bromine and nitrogen atoms, or a combination of these compounds. 4. The method of claim 1, wherein the ethylenically unsaturated comonomer is hexafluoropropylene or perfluoro(propyl vinyl ether). 5. Fluorine solvent is CCl_2FCClF_2 or C
2. The method of claim 1, wherein ClF_2CClF_2.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2200693A JP3006049B2 (en) | 1990-07-26 | 1990-07-26 | Method for removing low molecular weight polymer from melt-processable tetrafluoroethylene copolymer |
| EP19910112432 EP0472908A3 (en) | 1990-07-26 | 1991-07-24 | Removal of low molecular weight fractions of melt processable tetrafluoroethylene copolymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2200693A JP3006049B2 (en) | 1990-07-26 | 1990-07-26 | Method for removing low molecular weight polymer from melt-processable tetrafluoroethylene copolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0485305A true JPH0485305A (en) | 1992-03-18 |
| JP3006049B2 JP3006049B2 (en) | 2000-02-07 |
Family
ID=16428679
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2200693A Expired - Fee Related JP3006049B2 (en) | 1990-07-26 | 1990-07-26 | Method for removing low molecular weight polymer from melt-processable tetrafluoroethylene copolymer |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP0472908A3 (en) |
| JP (1) | JP3006049B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058833A1 (en) * | 2002-12-25 | 2004-07-15 | Daikin Industries, Ltd. | Fluoropolymer and composition thereof |
| US7192196B2 (en) | 2002-07-15 | 2007-03-20 | Tomoegawa Paper Co., Ltd. | Optical fiber connection component, optical fiber connection structure, and optical fiber connection method |
| JP2007535609A (en) * | 2004-04-30 | 2007-12-06 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Fluoropolymer with reduced smoke generation |
| JP2014501305A (en) * | 2010-12-23 | 2014-01-20 | スリーエム イノベイティブ プロパティズ カンパニー | Fluoropolymer composition and purification method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5237049A (en) * | 1992-08-28 | 1993-08-17 | E. I. Du Pont De Nemours And Company | Purification and adhesion of fluoropolymers |
| US5650472A (en) * | 1993-04-16 | 1997-07-22 | Daikin Industries, Ltd. | Fluorine-containing copolymer, process for preparing the same and fluorine-containing elastomer |
| JP2022028402A (en) | 2020-08-03 | 2022-02-16 | 三井・ケマーズ フロロプロダクツ株式会社 | Resin pellet, and molded product thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4360601A (en) * | 1980-12-10 | 1982-11-23 | E. I. Du Pont De Nemours And Company | Process for extraction of fluorinated copolymers with fluorocarbons |
-
1990
- 1990-07-26 JP JP2200693A patent/JP3006049B2/en not_active Expired - Fee Related
-
1991
- 1991-07-24 EP EP19910112432 patent/EP0472908A3/en not_active Withdrawn
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7192196B2 (en) | 2002-07-15 | 2007-03-20 | Tomoegawa Paper Co., Ltd. | Optical fiber connection component, optical fiber connection structure, and optical fiber connection method |
| KR100738783B1 (en) * | 2002-07-15 | 2007-07-12 | 가부시키가이샤 도모에가와 세이시쇼 | Optical fiber connection component, optical fiber connection structure, and optical fiber connection method |
| WO2004058833A1 (en) * | 2002-12-25 | 2004-07-15 | Daikin Industries, Ltd. | Fluoropolymer and composition thereof |
| US8137812B2 (en) | 2002-12-25 | 2012-03-20 | Daikin Industries, Ltd. | Fluoropolymer and composition thereof |
| US8202617B2 (en) | 2002-12-25 | 2012-06-19 | Daikin Industries, Ltd. | Fluoropolymer and composition thereof |
| JP2007535609A (en) * | 2004-04-30 | 2007-12-06 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Fluoropolymer with reduced smoke generation |
| JP2012233194A (en) * | 2004-04-30 | 2012-11-29 | E I Du Pont De Nemours & Co | Reduced fuming fluoropolymer |
| JP2014501305A (en) * | 2010-12-23 | 2014-01-20 | スリーエム イノベイティブ プロパティズ カンパニー | Fluoropolymer composition and purification method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3006049B2 (en) | 2000-02-07 |
| EP0472908A2 (en) | 1992-03-04 |
| EP0472908A3 (en) | 1992-05-13 |
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